Compositons of electrically conductive polymers and non-polymeric fluroinated organic acids

ABSTRACT

Compositions are provided comprising at least one conductive polymer and at least one non-polymeric fluorinated organic acid, salt or ester, wherein the conductive polymer is selected from a polythiophene, a polypyrrole, a polyaniline, and combinations thereof. Electronic devices and applications having at least one layer comprising such compositions are further provided.

RELATED APPLICATION DATA

This application is a division of application Ser. No. 10/823,320 filedApr. 13, 2004.

FIELD OF THE INVENTION

The invention relates to compositions comprising at least oneelectrically conducting polymer and at least one non-polymericfluorinated organic acid.

BACKGROUND OF THE INVENTION

Electrically conducting polymers have been used in a variety of organicelectronic devices, including in the development of electroluminescent(“EL”) devices for use in light emissive displays. With respect to ELdevices, such as organic light emitting diodes (OLEDs) containingconducting polymers, such devices generally have the followingconfiguration:

anode/buffer layer/EL material/cathode

The anode is typically any material that is transparent and has theability to inject holes into the EL material, such as, for example,indium/tin oxide (ITO). The anode is optionally supported on a glass orplastic substrate. EL materials include fluorescent dyes, fluorescentand phosphorescent metal complexes, conjugated polymers, and mixturesthereof. The cathode is typically any material (such as, e.g., Ca or Ba)that has the ability to inject electrons into the EL material.

The buffer layer is typically an electrically conducting polymer andfacilitates the injection of holes from the anode into the EL materiallayer. The buffer layer can also be called a hole-injection layer, ahole transport layer, or may be characterized as part of a bilayeranode. Typical conducting polymers employed as buffer layers includepolyaniline (“PAni”) and polydioxythiophenes such aspoly(3,4-ethylenedioxythiophene) (“PEDT”). These materials can beprepared by polymerizing aniline or dioxythiophene monomers in aqueoussolution in the presence of a water soluble polymeric acid, such aspoly(styrenesulfonic acid) (“PSSA”), orpoly(2-acrylamido-2-methyl-1-propanesulfonic acid) (“PAAMPSA”), asdescribed in, for example, U.S. Pat. No. 5,300,575 and published PCTapplication WO 02/065484. A well known PEDT/PSS material is Baytron®-P,commercially available from H. C. Starck, GmbH (Leverkusen, Germany).

There is a need for improved conductive polymers with goodprocessability and increased conductivity.

SUMMARY OF THE INVENTION

New compositions are provided comprising at least one conductive polymerand at least one non-polymeric fluorinated organic acid, wherein theconductive polymer is selected from a polythiophene, a polypyrrole, apolyaniline, and combinations thereof.

An electronic device is provided comprising at least one layercomprising a at least one new composition. Also provided is the use ofthe new composition in at least buffer of an electronic device

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE FIGURES

The invention is illustrated by way of example and not limited in theaccompanying figures.

FIG. 1 illustrates a cross-sectional view of one type of an electronicdevice that comprises a buffer layer comprising the new composition.

FIG. 2 illustrates a cross-sectional view of a thin film field effecttransistor that comprises an electrode comprising the new composition.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, new compositions are provided comprising at least oneconductive polymer and at least one non-polymeric fluorinated organicacid, wherein the conductive polymer is selected from a polythiophene, apolypyrrole, a polyaniline, and combinations thereof.

As used herein, the term “non-polymeric” is intended to mean a compoundhaving a molecular weight no greater than about 2000. As used herein,the term “fluorinated organic acid” is intended to mean an organiccompound having at least one acid group and at least one fluorine bondedto a carbon atom. The term encompasses partially fluorinated andperfluorinated materials.

The conductive polymers suitable for the new composition can behomopolymers, or they can be co-polymers of two or more respectivemonomers. The composition may comprise one or more different conductivepolymers and one or more different non-polymeric fluorinated organicacids. In one embodiment, the conductive polymer is selected from apolythiophene, a polypyrrole, a polyaniline, and combinations thereof.

Polythiophenes contemplated for use in the new composition compriseFormula I below:

wherein:

-   -   R¹ is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl,        alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,        alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio,        arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,        phosphoric acid, phosphonic acid, halogen, nitro, cyano,        hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, ether carboxylate, amidosulfonate, ether sulfonate, and        urethane; or both R¹ groups together may form an alkylene or        alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic        or alicyclic ring, which ring may optionally include one or more        divalent nitrogen, sulfur or oxygen atoms, and    -   n is at least about 4.

As used herein, the term “alkyl” refers to a group derived from analiphatic hydrocarbon and includes linear, branched and cyclic groupswhich may be unsubstituted or substituted. The term “heteroalkyl” isintended to mean an alkyl group, wherein one or more of the carbon atomswithin the alkyl group has been replaced by another atom, such asnitrogen, oxygen, sulfur, and the like. The term “alkylene” refers to analkyl group having two points of attachment.

As used herein, the term “alkenyl” refers to a group derived from analiphatic hydrocarbon having at least one carbon-carbon double bond, andincludes linear, branched and cyclic groups which may be unsubstitutedor substituted. The term “heteroalkenyl” is intended to mean an alkenylgroup, wherein one or more of the carbon atoms within the alkenyl grouphas been replaced by another atom, such as nitrogen, oxygen, sulfur, andthe like. The term “alkenylene” refers to an alkenyl group having twopoints of attachment.

As used herein, the following terms for substituent groups refer to theformulae given below: “alcohol” —R³—OH “amidosulfonate”—R³—C(O)N(R⁶)R⁴—SO₃Z “benzyl” —CH₂—C₆H₅ “carboxylate” —R³—C(O)O—Z“ether” —R³—O—R⁵ “ether carboxylate” —R³—O—R⁴—C(O)O—Z “ether sulfonate”—R³—O—R⁴—SO₃Z “urethane” —R³—O—C(O)—N(R⁶)₂

-   -   where all “R” groups are the same or different at each        occurrence and:        -   R³ is a single bond or an alkylene group        -   R⁴ is an alkylene group        -   R⁵ is an alkyl group        -   R⁶ is hydrogen or an alkyl group        -   Z is H, alkali metal, alkaline earth metal, N(R⁵)₄ or R⁵        -   Any of the above groups may further be unsubstituted or            substituted, and any group may have F substituted for one or            more hydrogens, including perfluorinated groups.

In one embodiment, in the polythiophene both R¹ together form—O—(CHY)_(m)—O—, where m is 2 or 3, and Y is the same or different ateach occurrence and is selected from hydrogen, alkyl, alcohol,amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ethersulfonate, and urethane. In one embodiment, all Y are hydrogen. In oneembodiment, the polythiophene is poly(3,4-ethylenedioxythiophene). Inone embodiment, at least one Y group is not hydrogen. In one embodiment,at least one Y group is a substituent having F substituted for at leastone hydrogen. In one embodiment, at least one Y group is perfluorinated.

Polypyrroles contemplated for use the new composition comprise FormulaII below.

where in Formula II:

-   -   n is at least about 4;    -   R¹ is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl,        alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,        alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio,        arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,        phosphoric acid, phosphonic acid, halogen, nitro, cyano,        hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, amidosulfonate, ether carboxylate, ether sulfonate, and        urethane; or both R¹ groups together may form an alkylene or        alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic        or alicyclic ring, which ring may optionally include one or more        divalent nitrogen, sulfur or oxygen atoms; and    -   R² is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl,        amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, ether carboxylate, ether sulfonate, and urethane.

In one embodiment, R¹ is the same or different at each occurrence and isindependently selected from hydrogen, alkyl, alkenyl, alkoxy,cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether,amidosulfonate, ether carboxylate, ether sulfonate, urethane, epoxy,silane, siloxane, and alkyl substituted with one or more of sulfonicacid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid,halogen, nitro, cyano, hydroxyl, epoxy, silane, or siloxane moieties.

In one embodiment, R² is selected from hydrogen, alkyl, and alkylsubstituted with one or more of sulfonic acid, carboxylic acid, acrylicacid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy,silane, or siloxane moieties.

In one embodiment, the polypyrrole is unsubstituted and both R¹ and R²are hydrogen.

In one embodiment, both R¹ together form a 6- or 7-membered alicyclicring, which is further substituted with a group selected from alkyl,heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate,ether sulfonate, and urethane. These groups can improve the solubilityof the monomer and the resulting polymer. In one embodiment, both R¹together form a 6- or 7-membered alicyclic ring, which is furthersubstituted with an alkyl group. In one embodiment, both R¹ togetherform a 6- or 7-membered alicyclic ring, which is further substitutedwith an alkyl group having at least 1 carbon atom.

In one embodiment, both R¹ together form —O—(CHY)_(m)—O —, where m is 2or 3, and Y is the same or different at each occurrence and is selectedfrom hydrogen, alkyl, alcohol, benzyl, carboxylate, amidosulfonate,ether, ether carboxylate, ether sulfonate, and urethane. In oneembodiment, at least one Y group is not hydrogen. In one embodiment, atleast one Y group is a substituent having F substituted for at least onehydrogen. In one embodiment, at least one Y group is perfluorinated.

Polyanilines contemplated for use in the new composition compriseFormula III or Formula IV below.

wherein:

-   -   n is at least about 4;    -   p is an integer from 0 to 4;    -   m is an integer from 1 to 5, with the proviso that p+m=5; and    -   R³ is independently selected so as to be the same or different        at each occurrence and is selected from alkyl, alkenyl, alkoxy,        cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy,        alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino,        dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl,        arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic        acid, halogen, cyano, or alkyl substituted with one or more of        sulfonic acid, carboxylic acid, halo, nitro, cyano or epoxy        moieties; or any two R³ groups together may form an alkylene or        alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic        or alicyclic ring, which ring may optionally include one or more        divalent nitrogen, sulfur or oxygen atoms.

In one embodiment, the polyaniline is unsubstituted and p=0.

The polythiophene and polypyrrole polymers formed by oxidativepolymerization are positively charged. In the conductive form ofpolyaniline at least some of the nitrogens are protonated, so that italso is positively charged. The positive charges are balanced bynegative ions used in the polymerization, usually acid anions.

Non-polymeric fluorinated organic acids contemplated for use in the newcompositions can be soluble or dispersible in aqueous or non-aqueousliquid media. In one embodiment, the non-polymeric fluorinated organicacid is selected from non-polymeric fluorinated sulfonic acids,non-polymeric fluorinated phosphoric acids, non-polymeric fluorinatedphosphonic acids, non-polymeric fluorinated carboxylic acids,non-polymeric fluorinated acrylic acids, and mixtures thereof. In oneembodiment, the non-polymeric fluorinated organic acid is highlyfluorinated. The term “highly fluorinated” is intended to mean that atleast 50% of the hydrogens attached to carbon atoms have been replacedby fluorine. In one embodiment, the non-polymeric fluorinated organicacid is perfluorinated. In one embodiment, the non-polymeric fluorinatedorganic acid is a fluoroether organic acid, fluoroamido organic acid, orfluoroamidoether organic acid. In one embodiment, the non-polymericfluorinated organic acid is perfluorinated.

As used herein, the following terms refer to the formulae given below:ether organic acid R⁵—O—R⁴—Q amido organic acid R⁵—C(O)N(R⁶)R⁴—Qamidoether organic acid R⁵—C(O)N(R⁶)R⁴—O—R⁴—Qwhere R⁴, R⁵, and R⁶ are as defined above, and Q is an acid group or anacid salt group. As used herein, the prefix “fluoro” is intended to meanthat at least one hydrogen has been replaced by a fluorine. The termincludes partially fluorinated and perfluorinated. In one embodiment, Qis selected from —SO₃Z, —CO₂Z, —PO₃Z, where Z is as defined above.

In one embodiment, the non-polymeric organic acid is afluoroethersulfonic acid having Formula V:R⁷—(O—CF₂CFR_(f))_(a)—O—CF₂CFR′_(f)SO₃H  (V)wherein R⁷ is a fluoroalkyl group, R_(f) and R′_(f) are independentlyselected from F, Cl or a perfluorinated alkyl group having 1 to 10carbon atoms, and a=0, 1 or 2. In one embodiment, R⁷ is a perfluorinatedalkyl group. In one embodiment, R⁷ is selected from difluoromethyl and1,1,2,2-tetrafluoroethyl.

Examples of fluoroethersulfonic acids having Formula V include, but arenot limited to2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid, 1,1,2,2-tetrafluoro-2-(perfluoroethoxy)ethanesulfonic acid, and2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonic acid.

The fluoroethersulfonic acids can be made from the correspondingsulfonyl fluoride by hydrolyzing to form the sulfonic acid. The sulfonylfluoride can be prepared according to known synthetic procedures. Theacids can also converted to alkali metal salts.

In one embodiment, the new composition comprises an aqueous dispersionof a conductive polymer and a non-polymeric fluorinated organic acid. Inone embodiment, the new composition comprises a non-aqueous dispersionof a conductive polymer and a non-polymeric fluorinated organic acid. Asused herein, the term “dispersion” refers to a continuous liquid mediumcontaining a suspension of minute particles. As used herein, the term“aqueous” refers to a liquid that has a significant portion of water,and in one embodiment it is at least about 40% by weight water.

The new compositions can be formed by adding together a conductivepolymer and a non-polymeric fluorinated organic acid. The newcompositions can also be formed by carrying out the polymerizationreaction to form a conductive polymer in the presence of a non-polymericfluorinated organic acid.

In one embodiment, the new composition is formed by combining a solutionor dispersion of a conductive polymer with a solution or dispersion of anon-polymeric fluorinated organic acid. In one embodiment, theconductive polymer is in the form of an aqueous dispersion and thenon-polymeric organic acid is in the form of an aqueous solution. In oneembodiment, the materials are blended using sonication ormicrofluidization to ensure mixing of the components.

The synthesis of thiophene, pyrrole, and aniline polymers is well knownand has been extensively described. Polymerization of thiophene monomershas been described in, for example, U.S. Pat. No. 5,300,575.Polymerization of aniline monomers has been described in, for example,U.S. Pat. No. 5,798,170.

In one embodiment, the conductive polymer is made by oxidativepolymerization of the monomer or monomers to form the conductivepolymer, in the presence of a soluble polymeric acid. The polymerizationis generally carried out in a homogeneous solution. In one embodiment,the polymerization is carried out in a homogeneous aqueous solution. Inanother embodiment, the polymerization for obtaining the electricallyconducting polymer is carried out in an emulsion of water and an organicsolvent. In general, some water is present in order to obtain adequatesolubility of the oxidizing agent and/or catalyst. Oxidizing agents suchas ammonium persulfate, sodium persulfate, potassium persulfate, and thelike, can be used. A catalyst, such as ferric chloride, or ferricsulfate may also be present. The resulting polymerized product will be asolution, dispersion, or emulsion of the conductive polymer. Thesolution, dispersion, or emulsion of the conductive polymer willhereinafter be collectively referred to as the “liquid conductivepolymer composition.”

Aqueous dispersions of polypyrrole and a non-polymeric organic acidanion are available commercially from Sigma-Aldrich (St. Louis, Mo.).Aqueous dispersions of poly(2,3-ethylendioxythiophene)/PSSA areavailable commercially from H.C. Starck, GmbH. (Leverkusen, Germany).Aqueous and non-aqueous dispersions of doped polyaniline, and dopedpolyaniline solids are available commercially from Covion OrganicSemiconductors GmbH (Frankfurt, Germany) or Ormecon (Ambersbek,Germany).

In one embodiment, the polymerization reaction to form the conductivepolymer is carried out in the presence of the non-polymeric fluorinatedorganic acid. The polymerization can be carried out as described above.In one embodiment, the polymerization is carried out in the presence ofthe non-polymeric fluorinated organic acid and an additional polymericacid. In one embodiment, the additional polymeric acid is a polymericsulfonic acid. In one embodiment, the polymeric sulfonic acid isselected from polystyrene sulfonic acid (“PSSA”) andpoly(2-acrylamido-2-methyl-1-propanesulfonic acid) (“PAAMPSA”).

In one embodiment, the new composition is in the form of an aqueousdispersion and further comprises a co-dispersing liquid. As used herein,the term “co-dispersing liquid” refers to a substance which is liquid atroom temperature and is miscible with water. As used herein, the term“miscible” means that the co-dispersing liquid is capable of being mixedwith water (at concentrations set forth herein for each particularco-dispersing liquid) to form a substantially homogeneous solution.

Co-dispersing liquids contemplated for use in the new composition aregenerally polar, water-miscible organic liquids. Examples of suitabletypes of co-dispersing liquids include, but are not limited to, ethers,cyclic ethers, alcohols, alcohol ethers, ketones, nitriles, sulfides,sulfoxides, amides, amines, carboxylic acids, and the like, as well ascombinations of any two or more thereof.

In one embodiment, the co-dispersing liquid comprises a liquid selectedfrom, n-propanol, isopropanol, methanol, butanol, 1-methoxy-2-propanol,dimethylacetamide, n-methyl pryrozole, 1,4-dioxane, tetrahydrofuran,tetrahydropyran, 4 methyl-1,3-dioxane, 4-phenyl-1,3-dioxane,1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane,2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2,5-dihydrofuran,1-methylpyrrolindine, 1-methyl-2-pyrrolidinone, dimethylsulfoxide, andcombinations of any two or more thereof.

In one embodiment, compositions are provided comprising non-aqueousdispersions of at least one conductive polymer and at least onenon-polymeric fluorinated organic acid. In one embodiment, thenon-aqueous composition is made by dispersing conductive polymer solidsand non-polymeric fluorinated organic acid solids in a non-aqueousliquid medium. In one embodiment, the non-aqueous composition is made bydispersing non-polymeric fluorinated organic acid solids in anon-aqueous solution or a non-aqueous dispersion of conductive polymer.In one embodiment, the non-aqueous composition is made by dispersingconductive polymer solids in a non-aqueous dispersion or a non-aqueoussolution of non-polymeric fluorinated organic acid. In one embodiment,the non-aqueous composition is made by combining a non-aqueous solutionor dispersion of conductive polymer with a non-aqueous solutions ordispersion of non-polymeric fluorinated organic acid. The twonon-aqueous media can be the same or different, as long as they aremiscible with each other in the desired proportions. In any of the aboveembodiments, the materials can be blended using sonication ormicrofluidization to ensure adequate mixing of the components.

Dispersions of electrically conductive polymers generally have a fairlylow pH due to the presence of acids in the oxidative polymerizationprocess. For example, aqueous poly(ethylenedioxythiophene) (“PEDT”)dispersions, Baytron®-P VP AI 4083 and CH8000, from H. C. Starck, GmbH,Leverkusen, Germany have a pH below 2. It is frequently desirable tohave aqueous dispersions of conductive polymers with a higher pH, as theacidity can be corrosive. With Baytron-P, adjusting the pH to higherlevels can have a deleterious effect on the electrical properties of theconductive polymer and their functional effectiveness as a buffer layerin OLEDs.

In new compositions comprising at least one electrically conductingpolymer and at least one non-polymeric fluorinated acid, it has beenfound that the pH can be adjusted without sacrificing electricalproperties. The pH can be adjusted using known techniques, for example,ion exchange, by titration with an aqueous basic solution, or additionof a solid alkali metal hydroxide or alkaline earth hydroxide. The newcompositions can have a pH adjusted from 1 to 8. Adjusting the pH tohigher, more neutral values, does not deleteriously affect theelectrical properties and device performance of the conductive polymersin the new composition, and in most cases improves those properties.

In one embodiment, the liquid conductive polymer composition iscontacted with at least one ion exchange resin under conditions suitableto remove decomposed species, side reaction products, unreactedmonomers, and ionic impurities, and to adjust pH. This can be carriedout at any point after the polymerization reaction to form theconductive polymer. Thus the treatment can be carried out on theas-synthesized conductive polymer, the conductive polymer after it iscombined with the non-polymeric fluorinated organic acid, the conductivepolymer after it is redispersed in a non-aqueous liquid medium withoutthe non-polymeric fluorinated organic acid, and the conductive polymerafter it is redispersed in a non-aqueous liquid medium with thenon-polymeric fluorinated organic acid. The liquid conductive polymercomposition can be contacted with at least one ion exchange resin beforeor after the addition of a co-dispersing liquid. In one embodiment, theliquid conductive polymer composition is contacted with a first ionexchange resin and a second ion exchange resin.

In another embodiment, the first ion exchange resin is an acidic, cationexchange resin, such as a sulfonic acid cation exchange resin set forthabove, and the second ion exchange resin is a basic, anion exchangeresin, such as a tertiary amine or a quaternary exchange resin.

Ion exchange is a reversible chemical reaction wherein an ion in a fluidmedium (such as an aqueous dispersion) is exchanged for a similarlycharged ion attached to an immobile solid particle that is insoluble inthe fluid medium. The term “ion exchange resin” is used herein to referto all such substances. The resin is rendered insoluble due to thecrosslinked nature of the polymeric support to which the ion exchanginggroups are attached. Ion exchange resins are classified as acidic,cation exchangers, which have positively charged mobile ions availablefor exchange, and basic, anion exchangers, whose exchangeable ions arenegatively charged.

Both acidic, cation exchange resins and basic, anion exchange resins arecontemplated for use in the new process. In one embodiment, the acidic,cation exchange resin is an organic acid, cation exchange resin, such asa sulfonic acid cation exchange resin. Sulfonic acid cation exchangeresins contemplated for use in the new process include, for example,sulfonated styrene-divinylbenzene copolymers, sulfonated crosslinkedstyrene polymers, phenol-formaldehyde-sulfonic acid resins,benzene-formaldehyde-sulfonic acid resins, and mixtures thereof. Inanother embodiment, the acidic, cation exchange resin is an organicacid, cation exchange resin, such as carboxylic acid, acrylic orphosphoric acid cation exchange resin. In addition, mixtures ofdifferent cation exchange resins can be used. In many cases, the basicion exchange resin can be used to adjust the pH to the desired level. Insome cases, the pH can be further adjusted with an aqueous basicsolution such as a solution of sodium hydroxide, ammonium hydroxide, orthe like.

In another embodiment, the basic, anionic exchange resin is a tertiaryamine anion exchange resin. Tertiary amine anion exchange resinscontemplated for use in the new compositions include, for example,tertiary-aminated styrene-divinylbenzene copolymers, tertiary-aminatedcrosslinked styrene polymers, tertiary-aminated phenol-formaldehyderesins, tertiary-aminated benzene-formaldehyde resins, and mixturesthereof. In a further embodiment, the basic, anionic exchange resin is aquaternary amine anion exchange resin, or mixtures of these and otherexchange resins.

The first and second ion exchange resins may contact the liquidconductive polymer composition either simultaneously, or consecutively.For example, in one embodiment both resins are added simultaneously to aliquid conductive polymer composition, and allowed to remain in contactwith the dispersion for at least about 1 hour, e.g., about 2 hours toabout 20 hours. The ion exchange resins can then be removed from thecomposition by filtration. The size of the filter is chosen so that therelatively large ion exchange resin particles will be removed while thesolution and smaller dispersion particles will pass through. The basic,anion exchange and/or acidic, cation exchange resins renders the acidicsites more basic, resulting in increased pH of the dispersion. Ingeneral, at least 1 gram of ion exchange is used per about 1 gram ofcomposition solids. In other embodiments, the use of the ion exchangeresin is used in a ratio of up to about 5 grams of ion exchange resin tocomposition solids, and depends on the pH that is to be achieved. In oneembodiment, about one gram of Lewatit® MP62 WS, a weakly basic anionexchange resin from Bayer GmbH, and about one gram of Lewatit® MonoPlusS100, a strongly acidic, sodium cation exchange resin from Bayer, GmbH,are used per gram of the new composition.

In another embodiment, more conductive dispersions are formed by theaddition of highly conductive additives to the new compositioncomprising at least one conductive polymer and at least onenon-polymeric fluorinated organic acid. In one embodiment, newcompositions with relatively high pH can be formed, and further comprisethe conductive additives, especially metal additives, which are notattacked by the acid in the dispersion.

In one embodiment, the new composition further comprises at least oneconductive additive at a weight percentage sufficient to reach thepercolation threshold. Examples of suitable conductive additivesinclude, but are not limited to conductive polymers, metal particles andnanoparticles, metal nanowires, carbon nanotubes, carbon nanopoarticles,graphite fibers or particles, carbon particles, and combinationsthereof. A dispersing agent may be included to facilitate dispersing ofthe conductive additives.

In one embodiment, the new compositions are deposited to formelectrically conductive or semiconductive layers which are used alone,or in combination with other electroactive materials, as electrodes,electroactive elements, photoactive elements, or bioactive elements. Asused herein, the terms “electroactive element”, “photoactive element”and “bioactive element” refer to elements which exhibit the namedactivity in response to a stimulus, such as an electromagnetic field, anelectrical potential, solar energy radiation, and a biostimulationfield.

In one embodiment, the new compositions are deposited to form bufferlayers in an electronic device. The term “buffer layer” as used herein,is intended to mean an electrically conductive or semiconductive layerwhich can be used between an anode and an active organic material. Abuffer layer is believed to accomplish one or more function in anorganic electronic device, including, but not limited to planarizationof the underlying layer, hole transport, hole injection, scavenging ofimpurities, such as oxygen and metal ions, among other aspects tofacilitate or to improve the performance of an organic electronicdevice.

The term “layer” or “film” refers to a coating covering a desired area.The area can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel. Films can be formed by any conventional depositiontechnique, including vapor deposition and liquid deposition. Typicalliquid deposition techniques include, but are not limited to, continuousdeposition techniques such as spin coating, gravure coating, curtaincoating, dip coating, slot-die coating, spray coating, and continuousnozzle coating; and discontinuous deposition techniques such as ink jetprinting, gravure printing, and screen printing.

In one embodiment, there are provided buffer layers deposited fromliquid compositions comprising at least one conductive polymer and atleast one non-polymeric fluorinated organic acid. In one embodiment, thebuffer layers are deposited from aqueous dispersions comprising at leastone conductive polymer and at least one non-polymeric fluorinatedorganic sulfonic acid. In another embodiment, the buffer layers aredeposited from aqueous dispersion comprising at least one conductivepolymer and at least one non-polymeric fluorinated organic acid, whereinthe conductive polymer is selected frompoly(3,4-ethylenedioxythiophene), unsubstituted polypyrrole, andunsubstituted polyaniline.

In another embodiment, there are provided buffer layers deposited fromliquid compositions comprising at least one conductive polymer and atleast one non-polymeric fluorinated organic acid, which further compriseat least one co-dispersing liquid. In one embodiment, the co-dispersingliquid is selected from n-propanol, isopropanol, t-butanol, methanoldimethylacetamide, dimethylformamide, N-methylpyrrolidone, ethyleneglycol, and mixtures thereof.

In another embodiment, there are provided buffer layers deposited fromaqueous dispersions comprising at least one conductive polymer and atleast one non-polymeric fluorinated organic acid, which dispersion isfurther blended with other water soluble or dispersible materials.Depending on the final application of the material, examples of types ofadditional water soluble or dispersible materials which can be addedinclude, but are not limited to polymers, dyes, coating aids, carbonnanotubes, metal nanowires and nanoparticles, organic and inorganicconductive inks and pastes, charge transport materials, piezoelectric,pyroelectric, or ferroelectric oxide nano-particles or polymers,photoconductive oxide nanoparticles or polymers, dispersing agents,crosslinking agents, and combinations thereof. The materials can besimple molecules or polymers. Examples of suitable other water solubleor dispersible polymers include, but are not limited to, polyacrylamide,polyvinylalcohol, poly(2-vinylpridine), poly(vinylacetate),poly(vinylmethylether), poly(vinylpyrrolidone), poly(vinylbutyral),poly(styrenesulfonic acid, and conductive polymers such aspolythiophenes, polyanilines, polyamines, polypyrroles, polyacetylenes,and combinations thereof.

In another embodiment, there are provided electronic devices comprisingat least one electrically conductive or semiconductive layer comprisingthe new composition. Organic electronic devices that may benefit fromhaving one or more layers made from the new composition include, but arenot limited to, (1) devices that convert electrical energy intoradiation (e.g., a light-emitting diode, light emitting diode display,or diode laser), (2) devices that detect signals through electronicsprocesses (e.g., photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e.g., a transistor or diode). Other uses for the newcompositions include coating materials for memory storage devices,antistatic films, biosensors, electrochromic devices, solid electrolytecapacitors, energy storage devices such as a rechargeable battery, andelectromagnetic shielding applications.

In one embodiment, the organic electronic device comprises anelectroactive layer positioned between two electrical contact layers,wherein at least one of the layers of the device includes the new bufferlayer. One embodiment is illustrated in one type of OLED device, asshown in FIG. 1, which is a device that has anode layer 110, a bufferlayer 120, an electroluminescent layer 130, and a cathode layer 150.Adjacent to the cathode layer 150 is an optionalelectron-injection/transport layer 140. Between the buffer layer 120 andthe cathode layer 150 (or optional electron injection/transport layer140) is the electroluminescent layer 130.

The device may include a support or substrate (not shown) that can beadjacent to the anode layer 110 or the cathode layer 150. Mostfrequently, the support is adjacent the anode layer 110. The support canbe flexible or rigid, organic or inorganic. Generally, glass or flexibleorganic films are used as a support. The anode layer 110 is an electrodethat is more efficient for injecting holes compared to the cathode layer150. The anode can include materials containing a metal, mixed metal,alloy, metal oxide or mixed oxide. Suitable materials include the mixedoxides of the Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group11 elements, the elements in Groups 4, 5, and 6, and the Group 8-10transition elements. If the anode layer 110 is to be light transmitting,mixed oxides of Groups 12, 13 and 14 elements, such as indium-tin-oxide,may be used. As used herein, the phrase “mixed oxide” refers to oxideshaving two or more different cations selected from the Group 2 elementsor the Groups 12, 13, or 14 elements. Some non-limiting, specificexamples of materials for anode layer 110 include, but are not limitedto, indium-tin-oxide (“ITO”), aluminum-tin-oxide, gold, silver, copper,and nickel. The anode may also comprise an organic material such aspolyaniline, polythiophene, or polypyrrole. The IUPAC number system isused throughout, where the groups from the Periodic Table are numberedfrom left to right as 1-18 (CRC Handbook of Chemistry and Physics,81^(st) Edition, 2000).

The anode layer 110 may be formed by a chemical or physical vapordeposition process or spin-coating process. Chemical vapor depositionmay be performed as a plasma-enhanced chemical vapor deposition(“PECVD”) or metal organic chemical vapor deposition (“MOCVD”). Physicalvapor deposition can include all forms of sputtering, including ion beamsputtering, as well as e-beam evaporation and resistance evaporation.Specific forms of physical vapor deposition include rf magnetronsputtering and inductively-coupled plasma physical vapor deposition(“IMP-PVD”). These deposition techniques are well known within thesemiconductor fabrication arts.

The anode layer 110 may be patterned during a lithographic operation.The pattern may vary as desired. The layers can be formed in a patternby, for example, positioning a patterned mask or resist on the firstflexible composite barrier structure prior to applying the firstelectrical contact layer material. Alternatively, the layers can beapplied as an overall layer (also called blanket deposit) andsubsequently patterned using, for example, a patterned resist layer andwet chemical or dry etching techniques. Other processes for patterningthat are well known in the art can also be used. When the electronicdevices are located within an array, the anode layer 110 typically isformed into substantially parallel strips having lengths that extend insubstantially the same direction.

The buffer layer 120 can be deposited onto substrates using anytechnique well-known to those skilled in the art.

The electroluminescent (EL) layer 130 may typically be any organic ELmaterial, including, but not limited to, fluorescent dyes, fluorescentand phosphorescent metal complexes, conjugated polymers, and mixturesthereof. Examples of fluorescent dyes include, but are not limited to,pyrene, perylene, rubrene, derivatives thereof, and mixtures thereof.Examples of metal complexes include, but are not limited to, metalchelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum(Alq3); cyclometalated iridium and platinum electroluminescentcompounds, such as complexes of Iridium with phenylpyridine,phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov etal., Published PCT Application WO 02/02714, and organometallic complexesdescribed in, for example, published applications US 2001/0019782, EP1191612, WO 02/15645, and EP 1191614; and mixtures thereof.Electroluminescent emissive layers comprising a charge carrying hostmaterial and a metal complex have been described by Thompson et al., inU.S. Pat. No. 6,303,238, and by Burrows and Thompson in published PCTapplications WO 00/70655 and WO 01/41512. Examples of conjugatedpolymers include, but are not limited to poly(phenylenevinylenes),polyfluorenes, poly(spirobifluorenes), polythiophenes,poly(p-phenylenes), copolymers thereof, and mixtures thereof.

The particular material chosen may depend on the specific application,potentials used during operation, or other factors. The EL layer 130containing the electroluminescent organic material can be applied usingany number of techniques including vapor deposition, solution processingtechniques or thermal transfer. In another embodiment, an EL polymerprecursor can be applied and then converted to the polymer, typically byheat or other source of external energy (e.g., visible light or UVradiation).

Optional layer 140 can function both to facilitate electroninjection/transport, and can also serve as a confinement layer toprevent quenching reactions at layer interfaces. More specifically,layer 140 may promote electron mobility and reduce the likelihood of aquenching reaction if layers 130 and 150 would otherwise be in directcontact. Examples of materials for optional layer 140 include, but arenot limited to, metal-chelated oxinoid compounds (e.g., Alq₃ or thelike); phenanthroline-based compounds (e.g.,2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (“DDPA”),4,7-diphenyl-1,10-phenanthroline (“DPA”), or the like); azole compounds(e.g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (“PBD” orthe like), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole(“TAZ” or the like); other similar compounds; or any one or morecombinations thereof. Alternatively, optional layer 140 may be inorganicand comprise BaO, LiF, Li₂O, or the like.

The cathode layer 150 is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode layer 150can be any metal or nonmetal having a lower work function than the firstelectrical contact layer (in this case, the anode layer 110). As usedherein, the term “lower work function” is intended to mean a materialhaving a work function no greater than about 4.4 eV. As used herein,“higher work function” is intended to mean a material having a workfunction of at least approximately 4.4 eV.

Materials for the cathode layer can be selected from alkali metals ofGroup 1 (e.g., Li, Na, K, Rb, Cs), the Group 2 metals (e.g., Mg, Ca, Ba,or the like), the Group 12 metals, the lanthanides (e.g., Ce, Sm, Eu, orthe like), and the actinides (e.g., Th, U, or the like). Materials suchas aluminum, indium, yttrium, and combinations thereof, may also beused. Specific non-limiting examples of materials for the cathode layer150 include, but are not limited to, barium, lithium, cerium, cesium,europium, rubidium, yttrium, magnesium, samarium, and alloys andcombinations thereof.

The cathode layer 150 is usually formed by a chemical or physical vapordeposition process. In general, the cathode layer will be patterned, asdiscussed above in reference to the anode layer 110. If the device lieswithin an array, the cathode layer 150 may be patterned intosubstantially parallel strips, where the lengths of the cathode layerstrips extend in substantially the same direction and substantiallyperpendicular to the lengths of the anode layer strips. Electronicelements called pixels are formed at the cross points (where an anodelayer strip intersects a cathode layer strip when the array is seen froma plan or top view).

In other embodiments, additional layer(s) may be present within organicelectronic devices. For example, a layer (not shown) between the bufferlayer 120 and the EL layer 130 may facilitate positive charge transport,band-gap matching of the layers, function as a protective layer, or thelike. Similarly, additional layers (not shown) between the EL layer 130and the cathode layer 150 may facilitate negative charge transport,band-gap matching between the layers, function as a protective layer, orthe like. Layers that are known in the art can be used. In addition, anyof the above-described layers can be made of two or more layers.Alternatively, some or all of inorganic anode layer 110, the bufferlayer 120, the EL layer 130, and cathode layer 150, may be surfacetreated to increase charge carrier transport efficiency. The choice ofmaterials for each of the component layers may be determined bybalancing the goals of providing a device with high device efficiencywith the cost of manufacturing, manufacturing complexities, orpotentially other factors.

The different layers may have any suitable thickness. In one embodiment,inorganic anode layer 110 is usually no greater than approximately 500nm, for example, approximately 10-200 nm; buffer layer 120, is usuallyno greater than approximately 250 nm, for example, approximately 50-200nm; EL layer 130, is usually no greater than approximately 100 nm, forexample, approximately 50-80 nm; optional layer 140 is usually nogreater than approximately 100 nm, for example, approximately 20-80 nm;and cathode layer 150 is usually no greater than approximately 100 nm,for example, approximately 1-50 nm. If the anode layer 110 or thecathode layer 150 needs to transmit at least some light, the thicknessof such layer may not exceed approximately 100 nm.

In organic light emitting diodes (OLEDs), electrons and holes, injectedfrom the cathode 150 and anode 110 layers, respectively, into the ELlayer 130, form negative and positively charged polar ions in thepolymer. These polar ions migrate under the influence of the appliedelectric field, forming a polar ion exciton with an oppositely chargedspecies and subsequently undergoing radiative recombination. Asufficient potential difference between the anode and cathode, usuallyless than approximately 12 volts, and in many instances no greater thanapproximately 5 volts, may be applied to the device. The actualpotential difference may depend on the use of the device in a largerelectronic component. In many embodiments, the anode layer 110 is biasedto a positive voltage and the cathode layer 150 is at substantiallyground potential or zero volts during the operation of the electronicdevice. A battery or other power source(s) may be electrically connectedto the electronic device as part of a circuit but is not illustrated inFIG. 1.

In one embodiment, OLEDs comprising at least one buffer layer depositedfrom the new composition have been found to have improved lifetimes. Inone embodiment the buffer layer is deposited using any solutionprocessing technique and is an aqueous dispersion in which the pH hasbeen adjusted to above about 2.0.

In one embodiment a pH neutral composition is used in at least one layerof an electronic device. In one OLED embodiment, the pH is adjusted soas to reduce etching of the ITO layer during device fabrication andhence much lower concentration of In and Sn ions diffusing into thepolymer layers of the OLED. Since In and Sn ions are suspected tocontribute to reduced operating lifetime this is a significant benefit.The lower acidity also reduces corrosion of the metal components of thedisplay (e.g. electrical contact pads) during fabrication and over thelong-term storage. PEDT/PSSA residues will interact with residualmoisture to release acid into the displays with resulting slowcorrosion.

The layer in an organic electronic device comprising the new compositionmay further be overcoated with a layer of conductive polymer appliedfrom a non-aqueous medium. The conductive polymer can facilitate chargetransfer and also improve coatability. Examples of suitable conductivepolymers include, but are not limited to, polyanilines, polythiophenes,polydioxythiophene/polystyrenesulfonic acid,polyaniline/polymeric-acid-colloids such as those disclosed inco-pending application Ser. No. 10/669,577,polythiophene/polymeric-acid-colloids such as those disclosed inco-pending application Ser. No. 10/669,494, polypyrroles,polyacetylenes, and combinations thereof. The composition comprisingsuch a layer may further comprise conductive polymers, and may alsocomprise dyes, carbon nanotubes, carbon nanoparticles, metal nanowires,metal nanoparticles, carbon fibers and particles, graphite fibers andparticles, coating aids, organic and inorganic conductive inks andpastes, charge transport materials, semiconductive or insulatinginorganic oxide particles, piezoelectric, pyroelectric, or ferroelectricoxide nano-particles or polymers, photoconductive oxide nanoparticles orpolymers, dispersing agents, crosslinking agents and combinationsthereof. These materials can be added to the new composition eitherbefore or after polymerization of the monomer and/or before or aftertreatment with at least one ion exchange resin.

In one embodiment, there are provided thin film field effect transistorscomprising electrodes made from the new composition. For use aselectrodes in thin film field effect transistors, the conductingpolymers and the liquids for dispersing or dissolving the conductingpolymers must be compatible with the semiconducting polymers and thesolvents for the semiconducting polymers to avoid re-dissolution ofeither conducting polymers or semiconducting polymers. Thin film fieldeffect transistor electrodes fabricated from conducting polymers shouldhave a conductivity greater than 10 S/cm. However, electricallyconducting polymers doped with non-polymeric organic acid anions onlyprovide conductivity in the range of 10 S/cm or lower. Thus, in oneembodiment, the electrodes comprise a conductive polymer selected frompolythiophenes, polypyrroles, and polyanilines doped with at least onenon-polymeric organic acid anion, and a fluorinated colloid-formingpolymeric sulfonic acid in combination with electrical conductivityenhancers such as metal nanowires, metal nanoparticles, carbonnanotubes, or the like. The new compositions may be used in thin filmfield effect transistors as gate electrodes, drain electrodes, or sourceelectrodes.

Another illustration of a use for the new composition, is the thin filmfield effect transistors, is shown in FIG. 2. In this illustration, adielectric polymer or dielectric oxide thin film 210 has a gateelectrode 220 on one side and drain and source electrodes, 230 and 240,respectively, on the other side. Between the drain and source electrode,an organic semiconducting film 250 is deposited. New aqueous dispersionscontaining nanowires or carbon nanotubes are ideal for the applicationsof gate, drain and source electrodes because of their compatibility withorganic based dielectric polymers and semiconducting polymers insolution thin film deposition. Since new compositions as a colloidaldispersion, less weight percentage of the conductive fillers is required(relative to compositions containing water soluble polymeric sulfonicacids) to reach percolation threshold for a desired or high electricalconductivity.

In another embodiment, there are provided field effect resistancedevices comprising one layer comprising the new composition. The fieldeffect resistance devices undergo reversible change of resistance in theconducting polymer films when subjected to a pulse of gate voltage asillustrated in pages 339-343, No. 2, 2002, Current Applied Physics.

In another embodiment, there are provided electrochromic displayscomprising at least one layer comprising the new composition.Electrochromic displays utilize change of color when thin film of thematerial is subjected to electrical potential.

In yet another embodiment, there are provided memory storage devicescomprising silicon chips top-coated with the new composition. Forexample, a write-once-read-many-times (WORM) memory is known in the arts(Nature, Page 166 to 169, vol 426, 2003). When information is recorded,higher voltages at certain points in the circuit grids of silicon chipsdestroys the conductive polymer at those points to create “zero” bitdata. The conductive polymer at the untouched points remainselectrically conductive and becomes “1” bit data.

In another embodiment, the new compositions are used to form coatingsfor biosensor or electromagnetic shielding applications.

In another embodiment, the new compositions can be used for antistaticcoatings for plastic and cathode ray tubes, electrode materials forsolid electrolyte capacitors, metal anti-corrosion coatings,through-hole plating of printed circuit boards, photodiodes,bio-sensors, photodetectors, rechargeable batteries, photovoltaicdevices, and photodiodes. In addition, examples of other applicationsfor the new compositions can be found in, for example, AdvancedMaterials, page 490 to 491, vol. 12, No. 7, 2000.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of the “a” or “an” are employed to describe elements andcomponents of the invention. This is done merely for convenience and togive a general sense of the invention. This description should be readto include one or at least one and the singular also includes the pluralunless it is obvious that it is meant otherwise.

The new compositions and their uses will now be described in greaterdetail by reference to the following non-limiting examples.

EXAMPLES Example 1

This example will illustrate preparation of three non-polymericfluoroethersulfonic acids, and their alkali metal salts:

The sulfonyl fluoride form of the following three fluoroethersulfonicacids will be made first according to designed synthetic procedures.Each of the sulfonyl fluorides will be hydrolyzed to form the sulfonicacid. The acids will be also converted to alkali metal salts dependingon their use in the following examples.

-   1)    2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonic    acid:-   2) 1,1,2,2-tetrafluoro-2-(perfluoroethoxy)ethanesulfonic acid:-   3) 2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonic    acid:

Example 2

This Example will illustrate the polymerization of3,4-ethylenedioxythiophene in the presence of2-[1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid, and polystyrenesulfonic acid, and organic light emitting diodesmade therewith.

12.52 g (25.97 mmoles) perfluorosulfonic acid, 660.57 g deionized waterwill be massed into a one liter jacketed three-necked round bottomflask. 15.95 g 30% polystyrenesulfonic acid solution (70,000 molecularweight from PolySciences, Inc.) will be added to the reactor as aco-acid. The mixture will be allowed to stir for 20° C. for 30 minutes.2.768 ml (25.973 mmoles) of Baytron-M (a trade name for3,4-ethylenedioxythiophene from H.C. Starck, MA, USA) will be added tothe mixture and allowed to stir for 15 more minutes before addition offerric sulfate and sodium persulfate. 7.55 g (31.709 mmoles) sodiumpersulfate will be first dissolved in 10 g deionized water in a glassvial and then transferred to the ration mixture while the mixture isbeing stirred. A stock solution of ferric sulfate will be made first bydissolving 0.0942 g ferric sulfate hydrate with deionized water to atotal weight of 20.8617 g. 7.30 g (0.0637 mmoles) of the ferric sulfatestock solution will be added to the reaction flask immediately after theaddition of the sodium persulfate solution. The polymerization will beallowed to proceed with stirring at about 20° C. controlled bycirculation fluid. The reaction will be terminated in about 12 hours byadding Lewatit® S100, a trade name from Bayer, Pittsburgh, Pa., forsodium sulfonate of crosslinked polystyrene, and Lewatit® MP62 WS, atrade from Bayer, Pittsburgh, Pa., for free base/chloride oftertiary/quaternary amine of crosslinked polystyrene. The two resinswill be washed first before use with deionized water separately untilthere is no color in the water. The resin treatment will proceed for atleast 4 hrs. The resulting slurry will then be suction-filtered througha Buchner Funnel containing two pieces of Whatman #4 filter paper. pHand conductivity of the dispersion will be determined.

The aqueous dispersion will be spin-coated onto an ITO substrate, andsequentially spin-coated with either light emitting Super Yellow fromCovion (Frankfurt, Germany) or Lumination Green from Dow ChemicalCompany (Midland, Mich., USA). A cathode of Ba/Al will then be vapordeposited on the light-emitting layer. The devices will be tested fordevice voltage, efficiency, and lifetime.

A second sample of the dispersion will be further treated with ionexchange resins or titrated with a basic aqueous solution to adjust thepH to a higher value for device fabrication and testing.

Example 3

This example will illustrate the blending of2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid with Baytron-P®, AI4083, by sonication, and additional treatmentfor achieving higher pH, and organic light emitting diodes madetherewith.

In this example, Baytron-P® AI4083 (solid: ˜2.6%; pH˜1.67) will be usedto form a blend with the perfluorosulfonic acid. AI4083 is an aqueousPEDT/PSSA dispersion from H. C. Starck, GmbH, Leverkusen, Germany. Thew/w ratio between PEDT/PSSA is 1:6.1.227 g perfluorosulfonic acid willbe added to 96.84 g Baytron-P in a 250 mL round bottom flask while beingstirred with a magnetic stirrer. Resulting dispersion will contain ˜3.8%solid in which the equivalent ratio between perfluorosulfonicacid/PEDT/PSSA will be 1.0/1.0/4.6. The “equivalent ratio” as usedherein is intended to mean the ratio of the number of acid equivalentsof the perfluorosulfonic acid to the number of monomer units of PEDTand/or polymeric acid anion. The entire dispersion will then besubjected to sonication. The dispersion will then be checked forparticle size using an AccuSizer Model 780A (Particle Sizing Systems,Santa Barbara, Calif.).

The aqueous dispersion will be spin-coated onto an ITO substrate, andsequentially spin-coated with either light emitting Super Yellow fromCovion (Frankfurt, Germany) or Lumination Green from Dow ChemicalCompany (Midland, Mich., USA). A cathode of Ba/Al will then be vapordeposited on the light-emitting layer. The devices will be tested fordevice voltage, efficiency, and lifetime.

A second sample of the dispersion will be further treated with ionexchange resins or titrated with a basic aqueous solution for achievinghigher pH for device fabrication and testing.

Example 4

This example will illustrate the blending of1,1,2,2-tetrafluoro-2-(perfluoroethoxy)ethanesulfonic acid withBaytron-P®, AI4083, by sonication, and additional treatment forachieving higher pH, and organic light emitting diodes made therewith.

In this example, Baytron-P® AI4083 (solid: ˜2.6%; pH˜1.67) will be usedto form a blend with the perfluorosulfonic acid. AI4083 is an aqueousPEDT/PSSA dispersion from H. C. Starck, GmbH, Leverkusen, Germany. Thew/w ratio between PEDT/PSSA is 1:6. 0.804 g perfluorosulfonic acid willbe added to 96.84 g Baytron-P® in a 250 mL round bottom flask whilebeing stirred with a magnetic stirrer. Resulting dispersion will contain3.40% solid in which the equivalent ratio between perfluorosulfonicacid/PEDT/PSSA will be 1.0/1.0/4.6. The “equivalent ratio” as usedherein is intended to mean the ratio of the number of acid equivalentsof the perfluorosulfonic acid to the number of monomer units of PEDTand/or polymeric acid anion. The entire dispersion will then besubjected to sonication. The dispersion will then be checked forparticle size using an AccuSizer Model 780A (Particle Sizing Systems,Santa Barbara, Calif.).

The aqueous dispersion will be spin-coated onto an ITO substrate, andsequentially spin-coated with either light emitting Super Yellow fromCovion (Frankfurt, Germany) or Lumination Green from Dow ChemicalCompany (Midland, Mich., USA). A cathode of Ba/Al will then be vapordeposited on the light-emitting layer. The devices will be tested fordevice voltage, efficiency, and lifetime.

A second sample of the dispersion will be further treated with ionexchange resins or titrated with a basic aqueous solution to adjust thepH to a higher value for device fabrication and testing.

Example 5

This example will illustrate blending of2-[1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid with an aqueous PAni dispersion from Ormecon (Ambersbek, Germany),sold by Covion (Frankfurt, Germany), and additional treatment forachieving higher pH, and organic light emitting diodes made therewith.

D1002W PAni from Ormecon is an electrically conducting polyaniline/PSSA(“doped-PAni”) dispersed in water. A selected amount of theperfluorosulfonica acid will be added to a known amount of D1002Wdispersion. The aqueous dispersion of doped-PAni/perfluorosulfonic acidwill be spin-coated onto an ITO substrate, and sequentially spin-coatedwith either light emitting Super Yellow from Covion (Frankfurt, Germany)or Lumination Green from Dow Chemical Company (Midland, Mich., USA). Acathode of Ba/Al will then be vapor deposited on the light-emittinglayer. The devices will be tested for device voltage, efficiency, andlifetime for comparison with the device made with as-is D1000W PAni.

A second sample of the dispersion of PAni/perfluorosulfonic acid will beadjusted to a higher pH for device fabrication and testing.

Example 6

This example will illustrate the blending of2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid with a commercial aqueous polypyrrole dispersion and additionaltreatment for achieving higher pH and organic light emitting diodes madetherewith.

A commercial aqueous polypyrrole composition (5%, w/w) from Aldrich(2003-2004 Cat # 48,255-2) is a conductive polypyrrole doped with anorganic acid (“doped-PPy”). This will be diluted with deionized waterdown to 2.5% w/w. The dilution will be necessary to obtain a viscosity,which will allow the use of reasonable spin rates (<5,000 RPM). Aselected amount of the perfluorosulfonic acid will be added to a knownamount of the diluted doped-PPy dispersion. Thedoped-PPy/perfluorosulfonic acid dispersion will be spin-coated onto anITO substrate. The dried layer will be sequentially spin-coated witheither light emitting Super Yellow from Covion (Frankfurt, Germany) orLumination Green from Dow Chemical Company (Midland, Mich., USA). Acathode of Ba/Al will then be vapor deposited on the light-emittinglayer. The devices will be tested for device voltage, efficiency, andlifetime.

A second sample of the dispersion of doped-PPy/perfluorosulfonic acidwill be adjusted to a higher pH for device fabrication and testing.

Example 7

This example will illustrate blending of2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid with a non-aqueous PEDT/PSSA dispersion, and organic light emittingdiodes made therewith:

An aqueous PEDT/PSSA dispersion will be prepared first beforereformulation to a non-aqueous PEDT/PSSA dispersion. The aqueousPEDT/PSSA dispersion will be made according to a procedure similar tothe procedure in Example 2 except without use of the perfluorosulfonicacid. As-prepared aqueous PEDT/PSSA dispersion will be isolated and keptpartially wet before re-dispersion with n-propanol, DMAc, or NMP. There-formulated non-aqueous PEDT/PSSA, (“doped-PEDT”) will be added with aselected amount of the perfluorosulfonic acid. The non-aqueousdoped-PEDT/perfluorosulfonic acid dispersion will be spin-coated onto anITO substrate, and sequentially spin-coated with either light-emittingSuper Yellow from Covion (Frankfurt, Germany) or Lumination Green fromDow Chemical Company (Midland, Mich., USA). A cathode of Ba/Al will thenbe vapor deposited on the light-emitting layer. The devices will betested for device voltage, efficiency, and lifetime.

A second sample of the dispersion of will be treated for achievinghigher pH for device fabrication and testing.

1. A composition comprising at least one conductive polymer and at leastone non-polymeric fluorinated organic acid, salt or ester, wherein theconductive polymer is selected from a polythiophene, a polypyrrole, apolyaniline, and combinations thereof, wherein said non-polymericfluorinated organic acid, salt or ester comprises at least onefluoroether organic acid, salt or ester having the following generalformula,R⁵—O—R⁴-Q, wherein R⁴ is an alkylene group, R⁵ is an alkyl group, andare the same or different at each occurrence, Q is selected from —SO₃Z,—CO₂Z, and —PO₃Z, Z is H, alkali metal, alkaline earth metal, N(R⁵)₄, orR⁵, any of R⁴ and R⁵ may, independently, be unsubstituted orsubstituted, and the prefix “fluoro” means that at least one hydrogen ofR⁴ or R⁵ has been replaced by fluorine, and includes partiallyfluorinated and perfluorinated.
 2. A composition according to claim 1,wherein the composition is an aqueous dispersion having a pH 1 and
 8. 3.A composition according to claim 1, wherein the polythiophene comprisesFormula I:

wherein: R¹ is independently selected so as to be the same or differentat each occurrence and is selected from hydrogen, alkyl, alkenyl,alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl,arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl,arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen,nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl,carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate,and urethane; or both R¹ groups together may form an alkylene oralkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring, which ring may optionally include one or more divalentnitrogen, sulfur or oxygen atoms, and n is at least about
 4. 4. Acomposition according to claim 1, wherein the polypyrrole comprisesFormula II:

wherein: n is at least about 4; R¹ is independently selected so as to bethe same or different at each occurrence and is selected from hydrogen,alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl,alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonicacid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol,benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ethersulfonate, and urethane; or both R¹ groups together may form an alkyleneor alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring, which ring may optionally include one or more divalentnitrogen, sulfur or oxygen atoms; and R² is independently selected so asto be the same or different at each occurrence and is selected fromhydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl,arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,ether, ether carboxylate, amidosulfonate, ether sulfonate, and urethane.5. A composition according to claim 1, wherein the polyaniline comprisesFormula III or Formula IV:

wherein: n is at least about 4; p is an integer from 0 to 4; m is aninteger from 1 to 5, with the proviso that p+m=5; and R³ isindependently selected so as to be the same or different at eachoccurrence and is selected from alkyl, alkenyl, alkoxy, cycloalkyl,cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl,arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl,arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted withone or more of sulfonic acid, carboxylic acid, halo, nitro, cyano orepoxy moieties; or any two R³ groups together may form an alkylene oralkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring, which ring may optionally include one or more divalentnitrogen, sulfur or oxygen atoms.
 6. A composition according to claim 1,wherein the non-polymeric fluorinated organic acid is selected fromnon-polymeric fluorinated sulfonic acids, non-polymeric fluorinatedphosphonic acids, non-polymeric fluorinated carboxylic acids,non-polymeric fluorinated acrylic acids, their salts or esters, andmixtures thereof.
 7. A composition according to claim 6, wherein saidnon-polymeric fluorinated organic acid is highly fluorinated.
 8. Acomposition according to claim 6, wherein said non-polymeric organicacid is perfluorinated.
 9. A composition according to claim 2, furthercomprising an additional material selected from polymers, dyes, carbonnanotubes, metal nanowires, metal nanoparticles, carbon nanoparticles,carbon fibers, carbon particles, graphite fibers, graphite particles,coating aids, organic conductive inks, organic conductive pastes,inorganic conductive inks, inorganic conductive pastes, charge transportmaterials, semiconductive inorganic oxide nano-particles, insulatinginorganic oxide nano-particles, piezoelectric nano-particles,pyroelectric nano-particles, ferroelectric oxide nano-particles,piezoelectric polymers, pyroelectric polymers, ferroelectric oxidepolymers, photoconductive oxide nanoparticles, photoconductive polymers,dispersing agents, crosslinking agents, and combinations thereof.
 10. Acomposition according to claim 2, further comprising at least oneco-dispersing liquid.
 11. A composition according to claim 10, whereinthe co-dispersing liquid is selected from ethers, cyclic ethers,alcohols, alcohol ethers, ketones, nitriles, sulfides, sulfoxides,amides, amines, carboxylic acids, and combinations thereof.
 12. Acomposition comprising at least one conductive polymer and at least onenon-polymeric fluorinated organic acid, wherein the conductive polymeris selected from a polythiophene, a polypyrrole, a polyaniline, andcombinations thereof; and wherein said non-polymeric fluorinated organicacid is a fluoroether sulfonic acid having Formula V:R⁷—(O—CF₂CFR_(f))_(a)—O—CF₂CFR′_(f)SO₃H  (V) wherein R⁷ is a fluoroalkylgroup, R_(f) and R′_(f) are independently selected from F, Cl or aperfluorinated alkyl group having 1 to 10 carbon atoms, and a=0, 1 or 2.13. A composition according to claim 12, wherein saidfluoroethersulfonic acid is selected from2-(1,1,2,3,3,3-hexafluoro-1-(perfluoroethoxy)propane-2-yloxy)-1,1,2,2-tetrafluoroethanesulfonicacid, 1,1,2,2-tetrafluoro-2-(perfluoroethoxy)ethanesulfonic acid, and2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonic acid.14. An electronic device comprising at least one layer comprising acomposition according to claim
 1. 15. An electronic device comprising atleast one layer comprising a composition according to claim
 12. 16. Anelectronic device comprising at least one layer comprising a compositionaccording to claim
 13. 17. A device according to claim 14, wherein atleast one layer comprising the composition of claim is a buffer layer.18. A device according to claim 15, wherein at least one layercomprising the composition of claim is a buffer layer.
 19. A deviceaccording to claim 16, wherein at least one layer comprising thecomposition of claim is a buffer layer.
 20. A device according to claim14, wherein the device is selected a photosensor, photoswitch,light-emitting diode, light-emitting diode display, photodetector,phototransistor, photoconductor, phototube, Infra-Red detector, diodelaser, electrochromic device, electromagnetic shielding device, solidelectrolyte capacitors, energy storage device, field effect resistancedevice, memory storage device, biosensor, photoconductive cell,photovoltaic device, solar cell, memory storage, antistatic film,electrochromic, solid electrolyte capacitors, energy storage,electromagnetic shield and diode.
 21. A thin film field effecttransistor comprising at least one electrode comprising the compositionof claim 1.